Multistage hydrocarbon cracking process



Feb. .24, 1948. F. w. SCHEINEMAN A 2,436,486

MULTI-STAGE HYDROCARBON CRACKING PROCESS Filed Feb. 27, 1942 2 sheets-Sheet 1 Re 97167222211? Gasesy P CT l O/ T 01g/ /''E/VYJATP Gasoline,

Feb. 24, 1948. F; W. SCHEINEMAN 2,435,486

MULTI-STAGE HYDROCARBONv CRCKI'NG PROCESS Fi-led Feb. 27, 1942 2 Sheets-Sheet 2 PECTOR meme Feb. V24, 194s MUL'IIS-TAGE HYDROCARBON CRACKING PROCESS Fred W. Scheineman, Chicago, Ill., assigner to Standard Oil Company, Chicago, Ill., a corporation o! Indiana Application February-*27, 1942. Serial No. 432,547

This invention relates to multi-stage hydrocarbon conversion systems and it pertains more particularly to a two-stage system for the manufacture of high octane number motor fuels from hydrocarbon charging stocks by means of a fluidtype catalytic conversion systeml This application is a continuation-impart of my copending application Serial No. 400,956, filed July 3, 1941.

A fluid-type catalytic conversion system is one in which a powdered catalyst effects conversion while suspended in a. gas or vapor stream. The catalyst is then separated from reaction gases lor vapors, stripped with an inert gas such as steam, and suspended in a gas mixture for regeneration. The regenerated catalyst is then separated from regeneration gases and resuspended in a gas or vapor stream for effecting" further conversion. My invention relates to improvements in this fluid-type catalytic conversion system-wherein the powdered catalyst effects conversion in two separate zones under very different operating conditions,

The activity of catalysts for effecting various types of conversion depends on a number of factors including the type of catalyst employed, the relative freshness of the catalyst or amount of carbonaceous material deposited thereon, the temperature of the conversion, etc. When a catalyst becomes excessively coated with carbonaceous material on initial contact with the charg` ing stock it may no longer possess the activity required for effecting theV desired conversion. The optimum temperature for the initial stages of the conversion may be very different than the temperatures required for the final stages in theV vproduction of high octane number motor fuels. The optimum catalyst-to-oil ratio for the initial stages of the conversion may likewise be very different from the optimum catalyst-to-oil ratio for the final stages. An object of my inventipn is to provide a unitary fluid-type system wherein a catalytic conversion may be eilected in 'stages so that the catalyst-to-oil ratio catalyst holding time, weight space velocity, temperature, etc. in each stage may be controlled entirely independently of the control in the other stage or stages.

A further object of my invention is to provide a fluid-type catalytic conversion system wherein there is .a lower percent of carbon on the catalyst in the secondary stage than can possibly be maintained in the single reactor systems heretofore employed. A further object is to maintain a substantially optimum carbonaceous deposit on the catalyst throughout the entire cracking range.

A further object is to provide a fluid-type catalytic conversion system which 'will be characterized by greater flexibility of operating conditions (such as temperature, pressure, catalyst-tooil ratios, catalyst residence time, space velocities, etc.) than has heretofore been possible in anyconversion system of this type. e

A further object is to provide a system wherein a liquid or only partially vaporized charging stock may be vaporized and partially cracked in a primary conversion stage with a very high catalyst-to-oil ratio and with a short time of contact and wherelnthe vapors iromthis first stage may be cracked in the second stage at a lower catalyst to-oil ratio with active catalyst to obtain a. motor fuel of the desired characteristics.

Other objects of the invention will be apparent as the detailed description proceeds.

A feature of my invention is the use of a single regener'ator with a plurality of conversion stages, the. catalyst iiow being from the regeneratio zone` to each stage and thence back to the regeneration zone and the charging .stock flow being in series through the two or more stages. When employing an unvaporized or only partially vaporized gas oil or residual oil charging stock, I may employ a very high catalyst-to-oil ratio, i. e., a catalyst-to-cil weight ratio within the approximate range of to 25, in the rst stage for effecting substantially complete vaporization and initial cracking and I may then conduct the vapors from this first stage to a second stageI wherein the catalyst-to-,oil weight ratio is relatively low, i. e., within the'approximate' range of l to 4.

'The catalyst holding time in the first stage may be very short, i. e., about one minute or less. while in the second stage it may be relatively long, i. e., about 3 to l0 minutes or more. While considerable carbonaceous material will be formed in the first stage the high catalyst-to-oil ratio will prevent the carbon deposit on the catalyst from exceeding about 4 or 5% by weight based on catalyst and in the second stage, even with the longer catalyst holding time, the carbon deposit on the catalyst will be substantially less than 5% and'lt may be only about l to 3%. By this multi-stage process the catalyst is used more effectively in each stage, excessive carbonacecus deposits are prevented, and consequently larger yields of high octane number gasoline is obtainable.

Where a gasoline of maximum clear octane number is desiredthe second stage may be at a higher temperature than the first stage. When a gasoline of maximum leaded octane number is desired the treating temperature in the second stage may be lower than that of the first stage.

The extent and character of the conversion is. however, dependent upon the activity of the catalyst and other operating conditions such as weight space velocity, catalyst-to-oil weight ratio, catalyst residence time, etc. so that temperature is not the sole factor which requires consideration. Nevertheless, temperature control is extremely important and a feature of my invention is the improved method and means for controlling the temperature in at least one of said conversion zones by regulating the amounts of relatively hot and relatively cool regenerated catalyst introduced thereto, my,

The invention will be more clearly understood from the following detailed description of specific examples read in coniunction with the accompanying drawings which form a part of this specification and vin which:

Figure l is a schematic dow diagram oi my improved multi-stage conversion system wherein both stages are operated at relatively high temperature, and

Figure 2 is a schematic flow diagram oi a multistaffe system wherein the second stage operates at a lower temperature than the first stage.

For catalytic cracking. I prefer to employ catalyst of the silica-alumina type. One example of such catalyst is acid treated montmorillonite clay commonly marketed as Super Filtrol. Another example is a synthetic catalyst consisting essentiallv nf activated silica with alumina either with or without additional metal oxides or iiucsilicaies. Such a catalyst may be prepared by ball milling silica hydrogel with alumina using about 2 to 30%,A

for example about 15%, of alumina. The ball milled dough may be dried at a temperature of about 240 F. and then activated by heating to a temperature of about 900 to 1000 F. Another method of preparing ahighly active cracking catalyst is to form a gel from dilute sodium silicate in the presence of an aluminum salt by the addition of excess dilute sulfuric acid. The resulting gel is boiled i'or an hour or two with an excess of am-l monioum hydroxide solution before washing, after which it is dried and heated as in the previous example. The silica-alumina catalyst may be rendered more stable at high temperatures by the addition thereto of zirconia or aluminum nuosilicate. Thoria, beryllium oxide or other metal oxides may also be included in the composition. My invention is not limited to the use of any particular catalyst and since no invention is claimed in the catalyst per se a further descrip-g tion thereof is unnecessary.

In these specific examples the catalyst is in powdered form with a particle size of about 10 to 100 microns. The invention is applicable to other catalyst sizes provided only that the catalyst be of such size and density that it may be aerated and handled as a uid in the manner herein described. The' bulk density of such catalyst which has settled for 5 or 10 minutes will usually range frorn30 to 45 pounds per cubic foot. With slight aeration', i. e., with gas or vapor velocities of about .O5 to .5 feet persecond, the bulk density of this catalyst is about 25 to 35 pounds per cubic foot and under such conditions the catalyst is referred to as "aerated catalyst. With vapor velocities of about 1 to 2 or 3 feet per second the bulk density of such catalyst may be from to 25 pounds per cubic foot. It is at such gas or vapor velocities that the powdered catalyst is maintained in the dense turbulent suspended catalyst phase which has been found most satisfactory for eiiecting cracking, treating and regeneration,

to be in the dilute, light or dispersed phase.

4 With higher and higher vapor velocities the bulk density becomes less and less. In zones above the level of dense phase catalyst in cracking, treating or regeneration zones, the average bulk density of catalyst is usually less than l pound per cubic foot and at such conditions the catalyst is said dilute phase may contain only about 50 grains or less of catalyst material per cubic foot.

In connection with Figure 1, I will describe the catalytic cracking oi' a heavy gas oil or reduced crude to produce high yields of a motor fuel of high clear octane number. It should be understood. of course, that the invention is -not limited to any particular type of charging stock and that instead of a virgin stock I may employ one which has undergone or been produced in a previous thermal or catalytic conversion. A1so,I may employ hydrocarbons produced by the hydrogenation of carbonaceous materials or by the synthesis of carbon monoxide with hydrogen (the so-called Fischer process) or by any other means.

This charging stock may be passed from source I0 by pump I I through coils I2 of pipe still I3. or it may be passed directly through line I4 to transfer line I5. Hot regenerated catalyst from standpipe I6 which is aerated by steam introduced through line Il, is introduced by means of valve 'I8 into transfer line I5. |The catalyst in standpipe I 6 may be at a temperature in the general vicinity of i000 l5'. and 5 to 25 parts by weight, for example about 15 parts by Weight. of this catalyst may be introduced into line I5 for each part by weight oi charging stock which is introduced thereto. Heavy charging stocks such as reduced crude, as is well known, cannot be completely vaporized without decomposition. If the charging stock is not completely vaporized when it meets this hot catalyst the contained heat of the catalyst immediately effects complete vaporization and the catalyst is carried by the charging stock vapors through transfer line I5 to reaction chamber I9, which may be an enlarged part of line I5 itself but which is preferably a vertical cylindrical vessel provided with an enlarged upper section 20. The reactor may be of such dimensions as to provide a vertical gas velocity therein Within the approximate range of about 1 to 3 feet per second so that the suspended catalyst therein is in turbulent dense phase condition. Considerable amounts of steam may be introduced with vthe charging stock or for injecting powdered catalyst into the transfer line or reactor. The temperature in the reactor may be within the approximate range of '750 to 950 F., for example about 850 F., and the pressure may be within the approximate range of atmospheric to about 50 pounds per square inch, for example about 10 pounds per square inch. This reactor should be of relatively small size so that the catalyst| residence time in the reactor will be less than one minute, for example in the general vicinity of 30 seconds, The space velocity will be relatively high, e., within the approximate range of 5 to 50 parts by weight of charging stock per hour charged to the reactor perpart by weight of catalyst in the reactor at any instant. The actual time of contact of the charging stock with the catalyst will thus be very short and over cracking will be prevented in spite of the severity of the operating conditions.

Catalyst may be withdrawn directly from the dense turbulent phase through stripper column 2i at the base of which steam is introduced through line 22. The 'catalyst then passes This picking up hot fresh regenerated catalyst from the base oi standpipe 32. The catalyst in this standpipe is aerated by steam from line 33. The amount of catalyst introduced into line 3I may be controlled by valve 34 and in thisparticular example I mayemploy a catalyst-to-oil weight ratio oi' about 1:1 to 4:1, for example about 3:1. Since the catalyst in the standpipe is at a temperature within the general vicinity of 1000 F. the suspended catalyst which is introduced by line 3| into reactor 35 may be at a temperature of about.800 to 1000 F., for example about 900 F. If desired I may pass the gases and vapors through line 36 and heating coil 31 before introducing them into line 3l for picking up hot regenerated catalyst from line 32.

Operating conditions in reactor 35 may be very different from those prevailing in reactor I9. The catalyst residence time in this reactor may be from about 2 to 30 minutes or more. for example about minutes. The space velocity is preferably within the approximate range of about 1 to 4 pounds of oil introduced per hour per pound of catalyst material in the reactor at any instant. The pressure in reactor may be substantially the same as that in reactor I9. Since the carbon deposition in reactor 35 is very much less than in reactor I9 (even at the higher temperature) the catalyst residence time may be considerably longer and the space velocity considerably lower than in the primary conversion stage. Under the conditions prevailing in reactor 35 a gasoline of very high octane number is produced and yields may be about or 50% based on initial charging stock.

Catalyst settles from reaction products in the enlarged upper portion 38 of reactor 35 and if necessary or desirable I may employ cyclone separators or other separation means for limiting the amount of catalyst which is carried overhead with gases and vapors throughline 39. The reaction products are then introduced into fractionating column 40 and any residualcatalyst material is scrubbed out in the lower part of this column and returned with heavy condensate by line 4I and pump 42 either through line 43 to heating coils I2 or through line 44 to heating coils 31. A por# tion of the heavy condensate from the bottom of the column may be recycled by pump 45 through cooler 46 to a point in the tower above the vapor inlet in order to effect the necessary cooling and scrubbing in the base of tower 40. Heavy gas oils may be withdrawn through line 41 and light gas oils through line 48.- Gasoline and gases are taken overhead through line 49 to a conventional system for separating water and for fractionating the hydrocarbons into a gasoline fraction, a, butane-butylene fraction and a gas fraction. It should be understood that these products may be fractionated in any known manner to separate products of desired boiling range but since this fractionation system per se forms no part of my invention it will not be describedinfurther detail.

lyst then passes through standpipe 52 which is.

aerated by steam introduced through line 53, it is discharged from the base of the standpipe in amounts regulated by valve 54, picked up by air introduced through line 55 and returned by line 58 back to regenerator 28. The regenerator is considerably larger than the reactors, i. e., it may have a volume five or ten times that ofconversion chamber 35. Air may be introduced into the base of the regenerator rthrough line 5'I`in such amounts that the verticall gas velocity in the re-` actor is within the approximate range of about 1 to 3 feet per second so that turbulent dense phase conditions will prevail throughout the main part of the regeneration zone. If necessary or desirable suitable cooling coils may be installed in the regenerator or catalyst may be withdrawn, passed through a cooler and then returned to the regenerator' for obtaining necessary temperature control. For catalyst of the silica-alumina -type the regenerator temperatures are generally held below 1050 F. although certain catalysts may safely withstand higher regeneration tem peratures.

Regeneration gases are withdrawn from the top of the regenerator through line 58. If necessary or desirable cyclone separators may be employed to prevent catalyst material from being taken overhead with regeneration gases but the enlarged settling zone at the top of the regenerator minimizes any tendency for catalyst to be taken overhead. Any residual catalyst material in the regeneration gases may berecovered by 4means of electrostatic precipitators or may oe scrubbed or filtered out of the gases in any known manner. The heat energy in these gases may be utilized for generating steam or driving a turbine or may be utilized in any' other known manner.

One portionof the regenerated catalyst passes through stripping section 60, is stripped with steam from line 3|, and is then passed through standpipe I6 for introduction into primary reactor I3. Another portion of the regenerated catalyst is removed through stripping section 62, stripped with steam introduced through line 83 and passes through standpipe 32 for introduction into the secondary reactor 35. The relative amounts of catalyst introducednto the primary and secondary reactors is determined by the position of valves I 8 and 34 respectively. Thus a high catalyst-to-oil ratio may be employed in the primary reactor I9 while a relatively low catalystfto-oil ratio is employed in reactor 35. The average amount of carbonaceous deposit on catalyst in reactor 35 will be substantially less than the average carbonaceous deposits on reactor I9 and theproducts which leave reactor I9 are materially improved in octane number by their subsequent passage through reactor35.

While I have described a preferred type of reactor it should be understood that my invention is not limited to any particular reactor design. Catalyst may be withdrawn from the base of the reactor o'r regenerator instead of from an interlyst transfer means may be of the type described in my copending applications'.

In connection with Figure 2, I will describe a system for the production of aviation gasoline of low acid heat from a charging stock of the heavy naphtha to light gas oil boiling range. In this case the charging stock from source I is passed by pump II through coils I2 of pipe still I3 or directly introduced through line I4 to transfer line I5 where it picks up regenerated catalyst from standpipe I6 as in the previous example. The catalyst-to-oil weight ratio entering reactor I9a as astream may be in the general vicinity of 5:1 and the temperature of the entering stream may be about 150 to 950 F., for example about 850 F. The weight space velocity in primary reactor I9a may be within the general vicinity of 2 or 3 pounds oi' charging stock per hour per pound of catalyst in this reactor and the residence time of the catalyst in the reactor may be in the general vicinity of about 5 minutes. Catalyst is withdrawn from this reactor directly from the dense phase and returned to the regenerator in the manner hereinabove described in connection with Figure 1.

In the production of aviation fuel where a high leaded octane number is desirable the second stage may be at a lower temperature than the rst stage and since freshly regenerated catalyst is desired in this second stage this catalyst must be cooled before it is suspended in the gases or .vapors leaving the i'lrst stage. Thus instead of introducing catalyst directly from the base of standpipe 32a into a hydrocarbon stream I may pick up this catalyst with air introduced through line 84 and convey the catalyst through tubes of cooler 65. Water or other uid may be intro"- duced around the tubes through line 66 and steam or other hot uids may be withdrawn through line 61. The cooled catalyst may then be introduced through..line 68 to cyclone sepa--v rator 69 and the separated catalyst may be withdrawn through standpipe 'IUI which is aerated by steam introduced through line 1I, the aeration steam serving to strip the oxygen out of the separated catalyst. This separated cooled catalyst is then introduced directly into rea"tor 35a in amounts controlled by valve 12. Reactor 35a may be superimposed directly over reactor I9a so that gases and vapors may pass directly through a suitable grating or distributing member 13 from the primary to the secondary reactor.

The catalyst-to-oil weight ratio in reactor 35a may vary throughout a relatively wide range, i. e., may be within the approximate range of 1 to 10 and will depend somewhat upon the catalyst-to-oil ratio employed in the first rea^tor I 9a. The catalyst-to-oil weight ratio in these two stages may be within the general vicinity of 5 or in the approximate vicinity of 1 to 10. The overall weight space velocity may be about 1/2 to 2 pounds or more per pound of charging stock per hour per pound of catalyst in the combined conversion zones at any instant. The catalyst residence time in secondary reactor 35a may likewise vary throughout a relatively wide range, i. e., from a minute or less to upwards of minutes. The temperature in the secondary stage may be within the approximate range of 550 to 750 F.,

cr example about 650 F.

The relatively cool catalyst leaving reactor 35a through standpipe 52a' will absorb a considerable amount of the heat of regeneration and thus facilitate temperature' control. The gases and residual catalyst from cyclone separator 69 may be retumed to the regenerator through line 14 and if desireda portion of the cooled catalyst may be returned therewith through line 15. It should be understood that catalyst cooler oi' the type illustrated by cooler 55 may be employed in the system hereinabove described in connection with Figure 1 and that a part of the cooled catalyst may be introduced into either of the conversion zones I9 or 35 in order to obtain the desired catalyst-to-oil ratios therein without exceeding desired operating temperatures.

While I have described in detail certain specic examples of my invention it should be understood that these examples are by way of illustration and not limitation. Numerous other modifications and alternative procedures will be apparent to those skilled in the art from the above description.

I claim:

1. The method of operating a catalytic cracking process employing iinely divided solid catalyst particles in a regeneration zone and two conversion zones which method comprises maintaining a dense turbulent catalyst phase superimposed by a dilute catalyst phase in the regeneration zone by passing regeneration gases upward in said zone at a low velocity, withdrawing hot catalyst directly from the dense turbulent catalyst phase in the regeneration zone to a first conversion zone, introducing a high boiling hydrocarbon charging stock at a low pointy in said first conversion zone at such a. rate as to maintain a dense turbulent catalyst phase therein, effecting only Partial cracking in said first conversion zone and employing a short catalyst residence time therein, withdrawing catalyst di rectly from the dense turbulent catalyst phase in the first conversion zone and returning it to the regeneration zone, removing conversion products from an upper part of the first conversion zone, withdrawing catalyst directly from the dense turbulent catalyst phase in the regeneration zone, cooling said withdrawn catalyst. introducing said cooled catalyst into a second conversion'zone, passing substantially al1 products produced in said first conversion zone to a low point in the second conversion zone at such a rate as to maintain a dense turbulent catalyst phase therein, effecting. further cracking in said second conversion zone and employing a longer catalyst residence time therein than is employed in said first conversion zone, withdrawing catalyst from the dense catalyst phase in the second conversion zone and returning it to said regeneration zone, removing products from an upper part of the second conversion zone and fractionating the removed products.

2. The method of operating a catalytic conversion system employing solid cracking catalyst having a particle size of about l0 to 100 microns for effecting the production of gasoline from a I charging stock that cannot be completely vaporized without decomposition, which method comprises preheating said charging stock without'.

completely vaporizing it, contacting said preheated stock with hot regenerated catalyst in an amount and at a temperature to complete the vaporization thereof, passing charging stock vapors upwardly through a first cracking zone at a velocity in the range of 1 to 3 feet per second effective for maintaining in said first cracking` zone a dense turbulent phase of catalyst superimposed by a light dispersed catalyst phase, employing conditions in said first cracking zone to eiiect only a partial cracking and to deposit lessv than 4% by weight of carbonaceous deposits on the catalyst, withdrawing a'v substantially 'catalyst-free gasiform stream from said dilute phase, withdrawing catalyst from a. point below the dense phase level in the first cracking zone to a regeneration zone, suspending another portion'of hot regenerated catalyst from the regeneration zone in said gasiformv streamandjpassing,:saidf stream upwardly in a second cracking zone at a velocity in the range of 1 to 9 feet per second ef.- fective for maintaining in said second cracking zone a dense turbulent catalyst phase superanposed by a light dilute catalyst phase, maintaining said second cracking zone.linden;conditions,` for effecting further cracking `of"cortiponerits'"di? said stream and for depositing onsail catalyst,

less than 3% by weight of carbon'aceous "rn'at'e' rial, withdrawing a ,substantially catalyst-free product stream from the light catalyst phase in the second cracking zone, withdrawing catalyst from the second cracking zone at a point below lthe dense phase level therein to said regeneration zone, passing a regeneration gas upwardly in the regeneration zone at ajvelocity in the range of 1 to` 3 feet per second effective for maintaining therein` a dense turbulent catalyst phase superimposed by a light dilute catalyst phase, withdrawing substantially catalyst-free' gases from said lastf v namedvdilute phase, maintaining a temperature in said regeneration zonev substantially higher than that inthe cracking4- zones whereby sensible heat is stored in the catalyst io use in said cracking zones, and withdrawing from below the dense phase level in said'regeneration zone hot regeneratedcatalyst lfor introduction to said rst and second crackingzonesrespectivelyn.,1v`

" FRED W'. SCHEINEMAN.

REFERENCES CITED The following' references are of'record 1n the le ofnthispatent: 

